CN106622183B - The preparation method and solid-phase micro-extraction fibre of solid-phase micro-extraction fibre - Google Patents

Abstract

The invention belongs to the technical field of instrument analysis, and particularly provides a preparation method of a novel solid phase microextraction fiber and the solid phase microextraction fiber. Prepared according to the following process steps: etching-organic solvent ultrasonic cleaning, drying-preparation of mixed solution A-preparation of sol solution B-immerse stainless steel wire in sequence in mixed solution A and sol solution B coating-aging-removal of capillary, and finally prepared A good new solid phase microextraction fiber has the advantages of firm coating and high extraction efficiency.

Description

Preparation method of solid phase microextraction fiber and solid phase microextraction fiber

technical field

The invention belongs to the technical field of instrument analysis, and particularly provides a preparation method of solid-phase micro-extraction fibers and solid-phase micro-extraction fibers.

Background technique

Solid phase microextraction (Solid phase Micro-Extration SPME) is a new extraction and separation technology developed on the basis of solid phase extraction. Compared with liquid-liquid extraction and solid phase extraction, it has short operation time and small sample volume. , without extraction solvent, suitable for analysis of volatile and non-volatile substances, good reproducibility and so on. Solid-phase microextraction fiber is the core component of solid-phase microextraction technology, but the existing solid-phase microextraction fiber has problems such as easy peeling off of the coating and low extraction efficiency.

Contents of the invention

In order to solve the above technical problems, the present invention provides a method for preparing solid phase microextraction fibers and solid phase microextraction fibers. The solid phase microextraction fibers prepared by this method have the advantages of firm coating and high extraction efficiency.

The present invention is achieved in that, according to one aspect of the present invention, a kind of preparation method of solid-phase microextraction fiber is provided, comprises the steps:

1) Put the stainless steel wire on the negative electrode of the stainless steel mesh of the plasma generator, connect the conductive rod to the positive electrode, set the voltage at 8-20kV, turn on the power supply, and process it in the plasma generator for 1min to 150min, so that the surface of the stainless steel wire is etched , increase the surface area, enhance its adsorption capacity, and generate hydroxyl, carbonyl and other free radicals at the same time;

2) Ultrasonic cleaning and drying of the stainless steel wire processed in step 1) with an organic solvent;

3) Take methacrylic acid, add trimethoxypropane, trimethacrylate, toluene, azobisisobutyronitrile, ultrasonically mix, and blow nitrogen to remove oxygen to obtain pre-polymerization mixed solution A; The above mixed solution is injected into a glass capillary for use;

4) Take 5 mg of reduced graphene oxide in a 1.5 mL centrifuge tube, add 300 μL of dimethylformamide, sonicate for 50-70 minutes until homogeneous, then add 50 μL of aminopropyltriethoxysilane and 100 μL of methyltrimethoxy Silane, ultrasonic 5min to mix, finally add 95% trifluoroacetic acid aqueous solution, ultrasonic 5min to homogeneous, the resulting solution is the sol solution B for preparing the solid phase microextraction coating, inject the above sol solution into the glass capillary with a micro injector ready for use;

5) Dip the treated stainless steel wire vertically into the prepared mixed solution A, and twitch slowly for 3-12 times to make it spread evenly; vertically immerse the stainless steel wire coated with the mixed solution A into the prepared sol solution B , slowly twitch 3-12 times to make it spread evenly;

6) Dry the stainless steel wire treated in step 5) under nitrogen protection for 24 hours, then put it into the gas chromatograph inlet for aging for 3 hours, and the temperature rises from 80°C to 280°C;

7) The capillary is removed to obtain the solid phase microextraction fiber.

Further, in step 1), the stainless steel wire is treated in the plasma generator for 60-120min.

Further, the organic solvent described in step 2) is one of acetone and ethanol.

Further, in step 3), toluene is the solvent, the concentration of methacrylic acid is 0.01mmol/L, the concentration of trimethoxypropane is 0.04mmol/L, the concentration of trimethacrylate is 0.04mmol/L 0.04, azobisisobutyl Nitrile concentration is 0.04mmol/L.

According to another aspect of the present invention, a solid phase microextraction fiber prepared according to the above method is also provided.

Compared with the prior art, the invention has the advantages that: the solid phase microextraction fiber coating prepared by the method is firm and has higher extraction efficiency.

Detailed ways

In order to make the object, technical solution and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.

Embodiment 1,

1) Put the stainless steel wire on the negative pole of the stainless steel mesh of the plasma generator, connect the conductive rod to the positive pole, set the voltage at 8kV, turn on the power supply, and process it in the plasma generator for 1min, so that the surface of the stainless steel wire is etched to increase the surface area, Enhance its adsorption capacity and generate hydroxyl, carbonyl and other free radicals at the same time;

2) Ultrasonic cleaning and drying of the stainless steel wire processed in step 1) with an organic solvent;

3) Take 0.01mmol of methacrylic acid, add 0.04mmol of trimethoxypropane, 0.04mmol of trimethacrylate 0.04mmol, 0.04mmol of azobisisobutyronitrile, dissolve in 100ml of toluene, ultrasonically mix, blow nitrogen to remove oxygen Afterwards, the pre-polymerization mixed solution A is obtained; the above-mentioned mixed solution is injected into a glass capillary with a micro-injector for stand-by;

4) Take 5 mg of reduced graphene oxide in a 1.5 mL centrifuge tube, add 300 μL of dimethylformamide, sonicate for 50 minutes until homogeneous, then add 50 μL of aminopropyltriethoxysilane and 100 μL of methyltrimethoxysilane, Ultrasonic for 5 minutes to mix, and finally add 95% trifluoroacetic acid aqueous solution, ultrasonic for 5 minutes to homogeneous, the obtained solution is the sol solution B for preparing the solid phase microextraction coating, inject the above sol solution into the glass capillary with a micro injector and wait use;

5) Immerse the treated stainless steel wire vertically into the prepared mixed solution A, and twitch slowly 3 times to make it evenly coated; vertically immerse the stainless steel wire coated with the mixed solution A into the prepared sol solution B, slowly Twist 3 times to make it spread evenly;

6) Dry the stainless steel wire treated in step 5) under nitrogen protection for 24 hours, then put it into the gas chromatograph inlet for aging for 3 hours, and the temperature rises from 80°C to 280°C;

7) The capillary is removed to obtain the solid phase microextraction fiber.

Embodiment 2,

1) Put the stainless steel wire on the negative pole of the stainless steel mesh of the plasma generator, connect the conductive rod to the positive pole, set the voltage at 20kV, turn on the power supply, and process it in the plasma generator for 150min, so that the surface of the stainless steel wire is etched to increase the surface area, Enhance its adsorption capacity and generate hydroxyl, carbonyl and other free radicals at the same time;

2) Ultrasonic cleaning and drying of the stainless steel wire processed in step 1) with an organic solvent;

3) Take 0.01mmol of methacrylic acid, add 0.04mmol of trimethoxypropane, 0.04mmol of trimethacrylate 0.04mmol, 0.04mmol of azobisisobutyronitrile, dissolve in 100ml of toluene, ultrasonically mix, blow nitrogen to remove oxygen Afterwards, the pre-polymerization mixed solution A is obtained; the above-mentioned mixed solution is injected into a glass capillary with a micro-injector for stand-by;

4) Take 5 mg of reduced graphene oxide in a 1.5 mL centrifuge tube, add 300 μL of dimethylformamide, sonicate for 70 minutes until homogeneous, then add 50 μL of aminopropyltriethoxysilane and 100 μL of methyltrimethoxysilane, Ultrasonic for 5 minutes to mix, and finally add 95% trifluoroacetic acid aqueous solution, ultrasonic for 5 minutes to homogeneous, the obtained solution is the sol solution B for preparing the solid phase microextraction coating, inject the above sol solution into the glass capillary with a micro injector and wait use;

5) Immerse the treated stainless steel wire vertically into the prepared mixed solution A, and twitch slowly for 12 times to make it spread evenly; vertically immerse the stainless steel wire coated with the mixed solution A into the prepared sol solution B, slowly Twitch 12 times to make it spread evenly;

6) Dry the stainless steel wire treated in step 5) under nitrogen protection for 24 hours, then put it into the gas chromatograph inlet for aging for 3 hours, and the temperature rises from 80°C to 280°C;

7) The capillary is removed to obtain the solid phase microextraction fiber.

Embodiment 3,

1) Put the stainless steel wire on the negative pole of the stainless steel mesh of the plasma generator, connect the conductive rod to the positive pole, set the voltage at 14kV, turn on the power supply, and process it in the plasma generator for 75min, so that the surface of the stainless steel wire is etched to increase the surface area, Enhance its adsorption capacity and generate hydroxyl, carbonyl and other free radicals at the same time;

2) Ultrasonic cleaning and drying of the stainless steel wire processed in step 1) with an organic solvent;

3) Take 0.01mmol of methacrylic acid, add 0.04mmol of trimethoxypropane, 0.04mmol of trimethacrylate 0.04mmol, 0.04mmol of azobisisobutyronitrile, dissolve in 100ml of toluene, ultrasonically mix, blow nitrogen to remove oxygen Afterwards, the pre-polymerization mixed solution A is obtained; the above-mentioned mixed solution is injected into a glass capillary with a micro-injector for stand-by;

4) Take 5 mg of reduced graphene oxide in a 1.5 mL centrifuge tube, add 300 μL of dimethylformamide, sonicate for 60 minutes until homogeneous, then add 50 μL of aminopropyltriethoxysilane and 100 μL of methyltrimethoxysilane, Ultrasonic for 5 minutes to mix, and finally add 95% trifluoroacetic acid aqueous solution, ultrasonic for 5 minutes to homogeneous, the obtained solution is the sol solution B for preparing the solid phase microextraction coating, inject the above sol solution into the glass capillary with a micro injector and wait use;

5) Immerse the treated stainless steel wire vertically into the prepared mixed solution A, and twitch slowly 7 times to make it spread evenly; vertically immerse the stainless steel wire coated with the mixed solution A into the prepared sol solution B, slowly Twist 7 times to make it spread evenly;

6) Dry the stainless steel wire treated in step 5) under nitrogen protection for 24 hours, then put it into the gas chromatograph inlet for aging for 3 hours, and the temperature rises from 80°C to 280°C;

7) The capillary is removed to obtain the solid phase microextraction fiber.

Claims (4)

1. the preparation method of solid-phase micro-extraction fibre, which is characterized in that include the following steps：

1) stainless steel wire is put on the cathode of plasma generator stainless (steel) wire, conductive rod connects anode, and voltage is arranged in 8- 20kV powers on, and 1~150min is handled in plasma generator, stainless steel wire surface is made to be etched, and increases surface Product, enhances its adsorption capacity, while generating hydroxyl, the free radicals such as carbonyl；

2) stainless steel wire handled well in step 1) is cleaned by ultrasonic with organic solvent, dried；

3) take 0.01mmol methacrylic acids, be added 0.04mmol trimethoxypropane gaves, 0.04mmol trimethyl acrylic esters, 100mL toluene, 0.04mmol azodiisobutyronitriles, ultrasonic mixing, nitrogen obtain prepolymerization mixed solution A after blowing down oxygen；With it is micro into Sample device will be for use in above-mentioned mixed liquor implantation glass capillary, wherein toluene is solvent, and methacrylic acid is a concentration of A concentration of 0.04mmol/L of 0.01mmol/L, trimethoxypropane gave, a concentration of 0.04mmol/L of trimethyl acrylic ester, azo two A concentration of 0.04mmol/L of isobutyronitrile；

4) it takes redox graphene 5mg in the centrifuge tube of 1.5mL, 300 μ L dimethylformamides, ultrasonic 50- is added Then 50 μ L aminopropyltriethoxywerene werenes and 100 μ L methyltrimethoxysilane, ultrasonic 5min is added to homogeneous in 70min Mixing, is eventually adding 95% trifluoroacetic acid aqueous solution, and for ultrasonic 5min to homogeneous, acquired solution is to prepare solid-phase micro-extraction coating Sol solution B, with microsyringe will in above-mentioned sol solution implantation glass capillary it is for use；

5) processed stainless steel wire is dipped vertically into prepared mixed solution A, slowly twitches under 3-12, makes its smearing Uniformly；The stainless steel wire for being coated with mixed solution A is dipped vertically into prepared sol solution B, slowly twitches under 3-12, makes It smears uniform；

6) by the stainless steel wire handled well in step 5), drying for 24 hours, is then placed in gas chromatograph injection port under nitrogen protection Aging 3h, temperature rise to 280 DEG C by 80 DEG C；

7) removal capillary is to get solid-phase micro-extraction fibre.

2. the preparation method of solid-phase micro-extraction fibre described in accordance with the claim 1, which is characterized in that stainless steel wire in step 1) 60-120min is handled in plasma generator.

3. the preparation method of solid-phase micro-extraction fibre described in accordance with the claim 1, which is characterized in that organic described in step 2) Solvent is one kind in acetone, ethyl alcohol.

4. a kind of solid-phase micro-extraction fibre prepared according to any methods of claim 1-3.